Orientation effects in copper phthalocyanine films studied by electron paramagnetic resonance spectroscopy

The metallo-phthalocyanines (MPcs) are an interesting group of organic semiconductor materials for applications such as large area solar cells due to their optoelectronic properties coupled with the possibility of easily and cheaply fabricating thin films of MPcs [1, 2]. As for organic semiconductors in general, many of the interesting properties of the MPcs such as magnetism, light absorption and charge transport, are highly anisotropic [2, 3]. To maximise the efficiency of a device based on these materials it is therefore important to study their molecular orientation in films and to assess the influence of different growth conditions and substrate treatments.
X-ray diffraction is a well established and powerful technique for studying texture (and hence molecular orientation) in crystalline materials, but it cannot provide any information about amorphous or nanocrystalline films. In electron paramagnetic resonance (EPR) spectroscopy the signal comes from the spin of unpaired electrons in the material. This technique therefore does not require the sample to be crystalline. It works for any sample with paramagnetic centres such as the MPcs where the unpaired electrons are contributed by the metal. In this paper we present a continuous-wave X-band EPR study using the anisotropy of the EPR spectrum of CuPc [4] to determine the orientation effects in different types of CuPc films. From these measurements we gain insight into the molecular arrangement of films with different spin concentrations, and apply our technique to the study of molecular orientation in photovoltaic cells.

Active sites on hydrogen evolution photocatalyst

Solar hydrogen production assisted with semiconductor materials is a promising way to provide alternative energy sources in the future. Such a photocatalytic reaction normally takes place on the active sites of the catalysts surface, and the identification of the active sites is crucial for understanding the photocatalytic reaction mechanism and further improving the photocatalytic efficiency. However, the active sites of model catalysts are still largely disputed because of their structural complexity. Conventionally, H-2 evolution from solar water splitting over Pt/TiO2 is widely deemed to take place on metallic Pt nanoparticles. Oppositely, we report through a combined experimental and theoretical approach, that metallic Pt nanoparticles have little contribution to the activity of photocatalytic H-2 evolution; the oxidized Pt species embedded on the TiO2 surface are the key active sites and primarily responsible for the activity of the hydrogen evolution Pt/TiO2 photocatalyst.

Surface plasmons in layered structures with semiconductor and metallic films

The complete spectrum of eigenwaves including surface plasmon polaritons (SPP), dynamic (bulk) and complex waves in the layered structures containing semiconductor and metallic films has been explored. The effects of loss, geometry and the parameters of dielectric layers on the eigenmode spectrum and, particularly, on the SPP modes have been analysed using both the asymptotic and rigorous numerical solutions of the full-wave dispersion equation. The field and Poynting vector distributions have been examined to identify the modes and elucidate their properties. It has been shown that losses and dispersion of permittivity qualitatively alter the spectral content and the eigenwave properties. The SPP counter-directional power fluxes in the film and surrounding dielectrics have been attributed to vortices of power flow, which are responsible for the distinctive features of SPP modes. It has been demonstrated for the first time that the maximal attainable slow-wave factor of the SPP modes guided by thin Au films at optical frequencies is capped not by losses but the frequency dispersion of the actual Au permittivity. © 2009 EDP Sciences.

Preparation, structural characterization, semiconductor and photoluminescent properties of zinc oxide nanoparticles in a phosphonium-based ionic liquid

A convenient microwave method in preparation of zinc oxide nanoparticles (ZnONPs) using an ionic liquid, trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide, [P-66614][NTf2], as a green solvent is described in this paper. To the best of our knowledge, there is no report for synthesizing any nanoparticle using this ionic liquid. Trihexyltetradecylphosphonium bis{(trifluoromethyl)sulfonyl}-imide has low interface tension and thus it can enhance the nucleation rate, which is favorable to the formation of smaller ZnONPs. The fabricated ZnONPs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis spectroscopy. The XRD pattern reveals that the ZnONPs have hexagonal wurtzite structure. The strong intensity and narrow width of ZnO diffraction peaks indicate that the resulting nanoparticles are of high crystallinity. The synthesized ZnONPs show direct band gap of 3.43 eV. The UV-vis absorption spectrum of ZnONPs dispersed in ethylene glycol at room temperature revealed a blue-shifted onset of absorption. (C) 2011 Elsevier Ltd. All rights reserved.

A comprehensive aerosol spray method for the rapid photocatalytic grid area analysis of semiconductor photocatalyst thin films

Indicator inks, previously shown to be capable of rapidly assessing photocatalytic activity via a novel photo-reductive mechanism, were simply applied via an aerosol spray onto commercially available pieces of Activ (TM) self-cleaning glass. Ink layers could be applied with high evenness of spread, with as little deviation as 5% upon UV-visible spectroscopic assessment of 25 equally distributed positions over a 10 cm x 10 cm glass cut. The inks were comprised of either a resazurin (Rz) or dichloroindophenol (DCIP) redox dye with a glycerol sacrificial electron donor in an aqueous hydroxyethyl cellulose (HEC) polymer media. The photo-reduction reaction under UVA light of a single spot was monitored by UV-vis spectroscopy and digital images attained from a flat-bed scanner in tandem for both inks. The photo-reduction of Rz ink underwent a two-step kinetic process, whereby the blue redox dye was initially reduced to a pink intermediate resorufin (Rf) and subsequently reduced to a bleached form of the dye. In contrast, a simple one-step kinetic process was observed for the reduction of the light blue redox dye DCIP to its bleached intermediates. Changes in red-green-blue colour extracted from digital images of the inks were inversely proportional to the changes seen at corresponding wavelengths via UV-visible absorption spectroscopy and wholly indicative of the reaction kinetics. The photocatalytic activity areas of cuts of Activ (TM) glass, 10 cm x 10 cm in size, were assessed using both Rz and DCIP indicator inks evenly sprayed over the films: firstly using UVA lamp light to activate the underlying Activ (TM) film (1.75 mW cm(-2)) and secondly under solar conditions (2.06 +/- 0.14 mW cm(-2)). The photo-reduction reactions were monitored solely by flat-bed digital scanning. Red-green-blue values of a generated 14 x 14 grid (196 positions) that covered the entire area of each film image were extracted using a Custom-built program entitled RGB Extractor(C). A homogenous degradation over the 196 positions analysed for both Rz (Red colour deviation = 19% UVA, 8% Solar: Green colour deviation = 17% UVA, 12% Solar) and DCIP (Red colour deviation = 22% UVA, 16% Solar) inks was seen in both UVA and solar experiments, demonstrating the consistency of the self-cleaning titania layer on Activ (TM). The method presented provides a good solution for the high-throughput photocatalytic screening of a number of homogenous photocatalytically active materials simultaneously or numerous positions on a single film; both useful in assessing the homogeneity of a film or determining the best combination of reaction components to produce the optimum performance photocatalytic film. (C) 2010 Elsevier B.V. All rights reserved.

Hybrid FIB milling strategy for the fabrication of plasmonic nanostructures on semiconductor substrates

The optical properties of plasmonic semiconductor devices fabricated by focused ion beam (FIB) milling deteriorate because of the amorphisation of the semiconductor substrate. This study explores the effects of combining traditional 30 kV FIB milling with 5 kV FIB patterning to minimise the semiconductor damage and at the same time maintain high spatial resolution. The use of reduced acceleration voltages is shown to reduce the damage from higher energy ions on the example of fabrication of plasmonic crystals on semiconductor substrates leading to 7-fold increase in transmission. This effect is important for focused-ion beam fabrication of plasmonic structures integrated with photodetectors, light-emitting diodes and semiconductor lasers.

Nonreciprocal scattering by stacked nonlinear magneto-active semiconductor layers

The combinatorial frequency generation by the periodic stacks of magnetically biased semiconductor layers has been modelled in a self-consistent problem formulation, taking into account the nonlinear dynamics of carriers. It is shown that magnetic bias not only renders nonreciprocity of the three-wave mixing process but also significantly enhances the nonlinear interactions in the stacks, especially at the frequencies close to the intrinsic magneto-plasma resonances of the constituent layers. The main mechanisms and properties of the combinatorial frequency generation and emission from the stacks are illustrated by the simulation results, and the effects of the individual layer parameters and the structure arrangement on the stack nonlinear and nonreciprocal response are discussed. © 2014 Elsevier B.V. All rights reserved.

Overview of the current ISO tests for photocatalytic materials

The current eight published ISO standards associated with semiconductor photocatalysis are considered. These standards cover: (1) air purification (specifically, the removal of NO, acetaldehyde and toluene), (2) water purification (the photobleaching of methylene blue and oxidation of DMSO) (3) self-cleaning surfaces (the removal of oleic acid and subsequent change in water droplet contact angle), (4) photosterilisation (specifically probing the antibacterial action of semiconductor photocatalyst films) and (5) UV light sources for semiconductor photocatalytic ISO work. For each standard, the background is first considered, followed by a brief discussion of the standard particulars and concluding in a discussion of the pros and cons of the standard, with often recommendations for their improvement. Other possible standards for the future which would either compliment or enhance the current ones are discussed briefly. 

Removal of microorganisms and their chemical metabolites from water using semiconductor photocatalysis

Semiconductor photocatalysis has been applied to the remediation of an extensive range of chemical pollutants in water over the past 30 years. The application of this versatile technology for removal of micro-organisms and cyanotoxins has recently become an area that has also been the subject of extensive research particularly over the past decade. This paper considers recent research in the application of semiconductor photocatalysis for the treatment of water contaminated with pathogenic micro-organisms and cyanotoxins. The basic processes involved in photocatalysis are described and examples of recent research into the use of photocatalysis for the removal of a range of microorganisms are detailed. The paper concludes with a review of the key research on the application of this process for the removal of chemical metabolites generated from cyanobacteria.

Application of laser radiation for the treatment of waste materials using a photocatalyst

One effective approach is to destroy industrial waste and pollution is the use of a semiconductor photocatalysis system. To date such, photocatalysis systems have employed conventional linear light sources. Initial results from a study of a photocatalysis system incorporating a tripled Nd:YAG laser are reported. The laser light not only played a roll as a light source for activating the photocatalyst(TiO₂), but also destroyed the organic species directly via a photochemical process. The reaction intermediates and changes in their concentrations are monitored using HPLC. The relationship between the power of laser and kinetics of photoreaction are discussed.

Nonreciprocal nonlinear scattering by stacked magnetoactive semiconductor layers

The combinatorial frequency generation by the periodic stacks of magnetically biased semiconductor layers has been modelled in the self-consistent problem formulation, taking into account the nonlinear dynamics of carriers. It has been shown that the nonlinear response of the magnetoactive semiconductor periodic structure is strongly enhanced by magnetic bias and combinations of the layer physical and geometrical parameters. The effects of the pump wave nonreciprocal reflectance and field displacement on the efficiency of three-wave mixing process is illustrated by the simulation results